JPH04345610A - Synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a water-soluble epoxy vinyl ester resin composition of excellent storage stability. CONSTITUTION:A bisphenol A epoxy resin and acrylic acid are subjected to an addition reaction, and the hydroxyl groups of the adduct and maleic anhydride are subjected to an addition reaction to obtain epoxy vinyl ester resin having a carboxyl groups in the molecule. Tributylamine and polyethylene glycol (200) diacrylate are added to the product to obtain an epoxy vinyl ester resin having amine salts of carboxyl groups in the molecule. A synthetic resin composition is prepared by adding N-nitrosophenyl-hydroxylaminate copper salt to the above resin. A water-soluble epoxy vinyl ester resin composition very excellent in storage stability can be obtained.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin composition having excellent storage stability.

0002

[Prior Art] Japanese Patent Application Laid-open No. 51-109988 states
Epoxy vinyl ester resins having an amine salt or ammonium salt of a carboxyl group in the side chain or terminal are described.

0003

[Problems to be Solved by the Invention] However, the above-mentioned epoxy vinyl ester resin had poor storage stability. The problem to be solved by the present invention is to provide an epoxy vinyl ester resin composition with excellent storage stability.

0004

[Means for Solving the Problems] As a result of intensive research to solve the problems of the prior art described above, the present inventors have discovered that the free carboxyl group of the reaction product of an epoxy vinyl ester resin and a polybasic acid anhydride The present inventors have discovered that adding a salt of N-nitrosohydroxylamines to a resin that has been neutralized with an amine or ammonium to form an amine salt or an ammonium salt greatly improves storage stability, and has completed the present invention. .

That is, the present invention provides a synthetic resin comprising an epoxy vinyl ester resin (A) having an amine salt or ammonium salt of a carboxyl group in the molecule, and a metal salt of N-nitrosohydroxylamines (B). Composition.

Epoxy vinyl ester resin (A) having an amine salt or ammonium salt of a carboxyl group in the molecule used in the present invention [hereinafter referred to as resin (A)]. ]
Any known and commonly used one can be used. Typical examples of the resin (A) include, for example, epoxy vinyl ester resin (A1) obtained by reacting an epoxy resin with an ethylenically unsaturated monobasic acid, and a polybasic acid anhydride (A2).
Examples include those in which the free carboxyl group of the reaction product is neutralized with an amine or ammonia (A3) to form an amine salt or an ammonium salt.

An example of the method for preparing resin (A) will be explained step by step. (1) First, the epoxy vinyl ester resin (A1) constituting the resin (A) will be explained. The epoxy vinyl ester resin (A1) is obtained by an esterification reaction between an epoxy group of an epoxy resin and a carboxyl group of an ethylenically unsaturated monobasic acid.

In this case, when carrying out the esterification reaction between the epoxy resin and the ethylenically unsaturated monobasic acid, the ratio of the epoxy resin to the ethylenically unsaturated monobasic acid is set to The unsaturated monobasic acid ranges from 0.8 to 1.1 equivalents, preferably from 0.90 to 1.1 equivalents.
The range is 0.05 equivalent moles. When the amount of the ethylenically unsaturated monobasic acid used is within the above range, gelation will not occur during the reaction process of the epoxy vinyl ester resin and the polybasic acid anhydride (A2), and the epoxy vinyl ester resin (
It is preferable because the reaction product of A1) and the polybasic acid anhydride (A2) has good storage stability. In particular, the free carboxyl group of the reaction product of the epoxy vinyl ester resin (A1) and polybasic acid anhydride (A2) is neutralized with amine or ammonia (A3), etc. to form an amine salt or ammonium salt ( The storage stability of A) deteriorates.

[0009] As the epoxy resin used to obtain the epoxy vinyl ester resin (A1) used in the present invention, any known and commonly used epoxy resin can be used, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac. Glycidyl ethers of polyhydric phenols such as type epoxy resins, cresol novolac type epoxy resins, and brominated epoxy resins; diglycidyl ethers of dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and alkylene oxide adducts of bisphenol A. Glycidyl ethers of polyhydric alcohols such as 3,4-
Epoxy-6-methylcyclohexylmethyl-3,4-
Alicyclic epoxy resins such as epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid diglycidyl ester , tetrahydrophthalic acid diglycidyl ester, diglycidyl p
-Glycidyl esters such as oxybenzoic acid and dimer acid glycidyl ester; tetraglycidyldiaminodiphenylmethane, tetraglycidyl m-xylylene diamine, triglycidyl P-aminophenol, N,N-
Glycidylamines such as diglycidylaniline; 1,
Heterocyclic epoxy resins such as 3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate; 2,2',4,4'-tetraglycidoxybiphenyl, dimethylbisphenol C diglycidyl ether, bisbeta trifluoro Special epoxy resins such as methyl diglycidyl bisphenol A and the like can be mentioned.

Examples of ethylenically unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl maleate, monopropyl maleate, monobutyl maleate, and mono(2- Examples include ethylhexyl) malate and sorbic acid.

[0011] In addition, in order to suppress side reactions in the esterification reaction between the epoxy resin and ethylenically unsaturated monobasic acid used in the present invention and to proceed with the esterification reaction efficiently, esterification may be carried out as necessary. A catalyst can be used. Examples of esterification catalysts include tertiary amines such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, dimethylaminomethylphenol, and tris(dimethylaminomethyl)phenol; tetramethylammonium chloride;
Quaternary ammonium salts such as tetramethylammonium bromide and triethylbenzylammonium chloride; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole; organic phosphine compounds such as triphenylphosphine; paratoluenesulfonate, etc. sulfonic acids; mercaptans;
Examples include metal halides such as lithium chloride.

The amount of the esterification catalyst used is usually 0.01 to 5.0 parts by weight, preferably 0.01 to 5.0 parts by weight, based on 100 parts by weight of the total weight of the epoxy resin and ethylenically unsaturated monobasic acid. 05 to 2.0 parts by weight.

[0013] Furthermore, during such an esterification reaction, it is preferable to use a polymerization inhibitor in order to prevent gelation during the production of the epoxy vinyl ester resin (A1). Examples of the polymerization inhibitor include hydroquinones such as hydroquinone, p-t-butylcatechol, 2,5-di-t-butylhydroquinone, and mono-t-butylhydroquinone; p-benzoquinone, naphthoquinone, phenanthraquinone, , 5-diphenyl-p-benzoquinone, and other phenols; hydroquinone monomethyl ether, di-t-butyl-p-cresol, and other phenols; phenothiazine, phenyl-β-naphthylamine, and other amines; copper naphthenate, and other copper salts etc. (2) Next, the reaction between the epoxy vinyl ester resin (A1) and the polybasic acid anhydride (A2) will be explained. This is a method of introducing free carboxyl groups into the epoxy vinyl ester resin (A1), and the hydroxyl groups generated in the epoxy vinyl ester resin (A1) by reacting the epoxy resin with an ethylenically unsaturated monobasic acid. By adding polybasic acid anhydride (A2), an epoxy vinyl ester resin having a free carboxyl group in the molecule can be obtained.

[0014] The epoxy vinyl ester resin (A1)
The ratio of the hydroxyl group and the polybasic acid anhydride (A2) is,
Hydroxyl group 1 of epoxy vinyl ester resin (A1)
The acid anhydride group of polybasic acid anhydride (A2) per equivalent is 0.3
It is preferable to use it in a range of 1.0 to 1.0 equivalents. When the amount of polybasic acid anhydride used is within the above range, the desired resin (A
) is preferable because it becomes sufficiently water-soluble, less unreacted polybasic acid anhydride remains in the resin (A), and the properties of the cured product are good.

Examples of the polybasic acid anhydride (A2) include maleic anhydride, succinic anhydride, itaconic anhydride,
Dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3 , 4-dimethyltetrahydrophthalic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, 3-butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-
Tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride, phthalic anhydride,
Examples include tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylcyclohexenedicarboxylic anhydride, and the like. (3) Next, a neutralization reaction between an epoxy vinyl ester resin having a free carboxyl group in its molecule and an amine or ammonia (A3) will be explained. The present invention can be achieved by adding amine or ammonia (A3) to the epoxy vinyl ester resin having a free carboxyl group in the molecule produced through the steps described above and neutralizing it to form a quaternary ammonium salt. An epoxy vinyl ester resin (A) having an amine salt or ammonium salt of a carboxyl group in the molecule used in is obtained. The ratio of the free carboxyl groups in the epoxy vinyl ester resin to the amine or ammonia (A3) is such that the ratio of the primary amino group of the amine, the secondary grade amino group, tertiary amino group or ammonia.
It is used in an amount of 4 to 1.5 equivalents, preferably 0.6 to 1.2 equivalents. When the amount of amine or ammonia (A3) used is within this range, the target resin (A) will be sufficiently water-soluble, and free amine or ammonia will be dissolved in the resin (A).
It is preferable because there is no fear that it will remain in the cured product and deteriorate the properties of the cured product.

Examples of amines used as a neutralizing agent include trimethylamine, triethylamine, N,N
-dimethylpropylamine, N,N-dimethylbutylamine, N-ethyl-N-methylbutylamine, tributylamine, tri-n-octylamine, tri-(2-ethylhexyl)amine, benzyldimethylamine, N,
N,N',N'-tetramethyldiaminomethane, N,N
, N',N'-tetramethyl-1,3-diaminopropane, triallylamine, N,N-dimethylallylamine, N-methyldiallylamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, butyldiethanolamine, 3-diethylamino- 1,2-propanediol, triethanolamine,
Tris(2-hydroxypropyl)amine, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-
Diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, (meth)acrylamide, N-methyl (meth)acrylamide, N,N
-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, (meth)acryloylmorpholine, N,N-dimethylaniline, N,
Tertiary amines such as N-diethylaniline, N-methylpiperidine, N-ethylpiperidine, N-methyl-3-piperidinemethanol, N-methyl-3-hydroxypiperidine, N-methylmorpholine, and acryloylmorpholine are preferred, and ammonia and Also used in the same way. Of course,
Dimethylamine, diethylamine, dipropylamine,
N-methylethylamine, diisobutylamine, diallylamine, diethanolamine, N-methylethanolamine, 2-(hydroxymethylamino)ethanol,
Secondary amines such as piperidine and primary amines such as methylamine, ethylamine, butylamine, hexylamine, and ethanolamine can also be used.

Next, the other component constituting the composition of the present invention, a salt of N-nitrosohydroxylamine (
B) will be explained. Salt (B) of N-nitrosohydrokylamine used in the present invention [hereinafter referred to as salt (B). ], any known and commonly used ones can be used; for example, N-nitrosophenylhydroxylamine copper salt, N-nitrosophenylhydroxylamine copper salt,
-Nitrosophenylhydroxylamine aluminum salt, N-nitrosophenylhydroxylamine iron salt, N-
Nitrosophenylhydroxylamine sodium salt, N
- Metal salts such as nitrosophenylhydroxylamine magnesium salt, N-nitrosophenylhydroxylamine calcium salt, N-nitrosophenylhydroxylamine triethylamine salt, N-nitrosophenylhydroxylamine trimethylamine salt, N-nitrosophenylhydroxylamine quaternary ammonium salt , amine salts such as N-nitrosophenylhydroxylamine benzyldimethylamine salt, and quaternary ammonium salts. As the salt (B), metal salts are more preferable than amine or ammonia salts because they can sufficiently improve the storage stability of the resin (A).

The amount of salt (B) used is 10
The amount is 0.01 to 3.0 parts by weight, preferably 0.05 to 1.0 parts by weight. When the amount of salt (B) used is within the above range, the curing time will not be delayed;
This is preferable because it provides a composition that has good storage stability and is highly economical.

Furthermore, it is of course possible to use water, a polymerizable vinyl monomer, or an organic solvent as a diluent, if necessary. Here, examples of the polymerizable vinyl monomers mentioned above include styrene, vinyltoluene,
Aromatic vinyl compounds such as p-methylstyrene, α-methylstyrene, t-butylstyrene, halogenated styrene, divinylbenzene; vinyl (meth)acrylate, vinyl crotonate, vinyl pivalate, vinyl 2-ethylhexanoate, Vinyl laurate, divinyl adipate,
Carboxylic acid vinyl esters such as vinyl benzoate and vinyl cinnamate; Allyl monomers such as allyl alcohol, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, diallyl maleate, diallyl phthalate, and triallyl isocyanurate; 2-ethylhexyl ( meth) acrylate, lauryl (meth)
Acrylate, cyclohexyl (meth)acrylate,
(meth)acrylate, such as tetrahydrofurfuryl (meth)acrylate, isophronyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, etc.
Esters of meth)acrylic acid; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate;
Alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl(meth)acrylate and ethoxyethyl(meth)acrylate; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate
acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Alkylene polyol poly(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, polyethoxylated trimethylolpropane tri(meth)acrylate, polypropoxylated trimethylolpropane Tri(meth)acrylate, polyethoxylated bisphenol A di(meth)acrylate, polypropoxylated bisphenol A di(meth)acrylate, polyethoxylated hydrogenated bisphenol A di(meth)acrylate, polypropoxylated hydrogenated bisphenol A di(meth)acrylate acrylate,
Polyoxyalkylene glycol poly(meth)acrylates such as polyethoxylated dicyclopentanyl di(meth)acrylate, polypropoxylated dicyclopentanyl di(meth)acrylate; hydroxypivalic acid neopentyl glycol ester di(meth)acrylate, etc. Ester-type poly(meth)acrylates; Isocyanurate-type poly(meth)acrylates such as tris[(meth)acryloxyethyl]isocyanurate; N,N-dimethylaminoethyl (meth)acrylate, N,N- Aminoalkyl (meth)acrylates such as dimethylaminopropyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate; (meth)acrylamide, N-methyl (meth)acrylamide , N,N-dimethyl(meth)acrylamide, N,N-
Examples include (meth)acrylamides such as dimethylaminopropyl (meth)acrylamide and (meth)acryloylmorpholine; allylamines such as triallylamine, N,N-dimethylallylamine, and N-methyldiallylamine; and vinylpyrrolidone. As the polymerizable vinyl monomer used in combination with the resin (A), water-soluble polymerizable vinyl monomers are preferred, and among them, water-soluble polymers such as hydroxyalkyl (meth)acrylates, polyoxyalkylene glycol poly(meth)acrylates, and vinylpyrrolidone are preferred. Particularly preferred are polymerizable vinyl monomers. Furthermore, aminoalkyl (meth)acrylates, (meth)acrylamides, allylamines, and the like are preferable because they can be used both as a neutralizing agent and as a polymerizable vinyl monomer.

On the other hand, typical organic solvents include aromatic hydrocarbons such as toluene and xylene; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate; , 4-dioxane, tetrahydrofuran, and other ketones; methyl ethyl ketone, methyl isobutyl ketone, and other ketones; ethylene glycol monomethyl ether, ethylene glycol monoethyl acetate, ethylene glycol monobutyl ether, and other glycol derivatives; cyclohexanone, cyclohexanol, and other cycloaliphatic These include hydrocarbons and petroleum solvents such as petroleum ether and petroleum naphtha.

[0021] The diluent may be used alone or in a mixture of two or more. The amount used is the resin (A)
The amount is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of solid content.

By the way, the composition of the present invention can be sufficiently cured simply by heating without using a curing catalyst, but an organic peroxide may be used if necessary. Furthermore, by using a photopolymerization initiator, it is also possible to cure with active energy rays such as ultraviolet rays and electron beams.

Examples of organic peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, t-butyl hydroperoxide, and dicumyl peroxide. oxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone, and the like.

Examples of photopolymerization initiators include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketal; acetophenone;
2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 2,2-diethoxy-
2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]
Acetophenones such as -2-morpholino-propan-1-one; methylanthraquinone, 2-ethylanthraquinone, 2-tasharybutylanthraquinone, 1-
Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4
- Thioxanthone such as dichlorothioxanthone, 2-methylthioxanthone, 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; Benzophenones such as benzophenone, 4,4-bismethylaminobenzophenone, and azo There are compounds, etc. These can be used alone or as a mixture of two or more, and further include tertiary amines such as triethanolamine and methyldiethanolamine;
- Can be used in combination with photoinitiation aids such as benzoic acid derivatives such as ethyl dimethylaminobenzoate. The amount of organic peroxide and photopolymerization initiator used is 0.5 to 20 parts by weight per 100 parts by weight of the polymerizable component in the composition.
Parts by weight, preferably 1 to 15 parts by weight.

Furthermore, various additives can be added to the composition of the present invention as required. Examples of the additives include fillers such as talc, barium sulfate, silica, and clay; thixotropy agents such as Aerosil; colorants; silicone, fluorine-based leveling agents, and antifoaming agents.

The composition of the present invention can be used as a water-soluble ultraviolet curable paint, an ultraviolet curable ink, a solder resist ink,
It can be used not only as a water-developable liquid photo solder, but also for cast molding, civil engineering adhesives, electrical insulation, and composite materials.

[0027] In recent years, environmental pollution caused by organic solvents, such as the destruction of the ozone layer by fluorocarbon gas, has become a social problem.
In addition, from the perspective of resource conservation, research is underway to eliminate or reduce the use of organic solvents in various fields and applications, and in the paint field in particular, progress is being made toward water-based paints, high solids paints, and UV paints. I'm here. In line with this trend, epoxy vinyl ester resins can be cured by ultraviolet light, so they can be used for UV-curable paints such as OP varnishes, hard coats for plastics, base coats for metal cans, and wood paints; various UV-curable printing inks; It is currently widely used as solder resist ink for wiring boards. In the field of these UV-curable paints, UV-curable inks, and solder resist inks, there has recently been a demand for water-soluble UV-curable paints, inks, resist inks, and the like. For example, organic solvents are currently used to clean equipment that uses UV-curable paints and inks for painting and printing. There is a movement toward cleaning these devices with water, and there is therefore a growing demand for water-soluble ultraviolet curable paints, ultraviolet curable inks, and solder resist inks. Furthermore, in the solder resist ink for printed wiring boards used in industrial equipment such as computers, instead of the screen printing type solder resist whose main component is epoxy resin, solvent-developed or alkaline-developed liquid photo solder is currently being used. has been put on the market, and the demand for it is rapidly increasing, but as mentioned above, due to the social background, the mainstream is shifting from solvent-developed liquid photosolder to alkali-developed liquid photosolder. However, due to the complexity of managing the alkaline concentration of the developer, research has been progressing on water-developable liquid photosolders that can be developed with water without the need to manage the concentration of an aqueous alkaline solution. There is.

The composition of the present invention was developed in view of the current situation, and has significantly improved storage stability of conventional water-developable compositions. Next, the present invention will be explained with reference to examples, but these are only one aspect and the present invention is not limited only by the examples. All parts and percentages in the text are based on weight.

[0029]

【Example】

Synthesis Example 1 370 parts of "Epicron 850" (bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals Co., Ltd., epoxy equivalent: 185) was placed in a 4-necked flask equipped with a stirrer, a cooler, a thermometer, a gas inlet tube, and a heating device. (2 equivalents) and 144 parts (2 equivalents) of acrylic acid, based on the total weight,
0.26 parts of hydroquinone, 1.5 parts of triethylamine
When the acid value reached 3, 176 parts (1.8 equivalents) of maleic anhydride was added and the reaction was carried out at 90°C for 1 hour, and 682 parts of polyethylene glycol 200 diacrylate was added. The mixture was cooled to 60° C., and 333 parts (1.8 equivalents) of tributylamine was added to neutralize the mixture to obtain a water-soluble resin solution A. Synthesis Example 2 Using the same equipment as in Synthesis Example 1, “Epicron N-740
(360 parts (2 equivalents) of phenol novolac type epoxy resin manufactured by the same company, epoxy equivalent: 180) and 1 part of acrylic acid.
44 parts (2 equivalents) were charged, 0.25 parts of hydroquinone and 1.51 parts of triethylamine were added to the total weight, and the mixture was reacted at 110°C for 8 hours. When the acid value reached 4, 160 parts of succinic anhydride was added. (1.6 equivalents) and add 90
The reaction mixture was allowed to react for 1 hour at °C, diluted with 834 parts of trimethylolpropane triacrylate, cooled to 60 °C, and neutralized by adding 170 parts (1.28 equivalents) of ethyldiethanolamine to obtain water-soluble resin solution B. Synthesis Example 3 430 parts of "Epicron N-680" (cresol novolak type epoxy resin manufactured by the same company, epoxy equivalent 215) (
2 equivalents) of pentaerythritol triacrylate 20
Then, 137 parts (1.9 equivalents) of acrylic acid was added, and 0.0 parts of hydroquinone was added to the total weight.
38 parts of triethylamine and 2.3 parts of triethylamine were added and reacted at 110°C for 8 hours. When the acid value reached 2, 193 parts (1.2 equivalents) of tetrahydrophthalic anhydride was added and reacted at 90°C for 2 hours to give pentane. Diluted with 333 parts of erythritol triacrylate, cooled to 60°C, and diluted with 4 parts of ammonia water.
0 part (1.0 equivalent as NH3) was added to neutralize the solution, and a water-soluble resin solution C was obtained. Example 1 A synthetic resin composition was obtained by adding 0.08 parts of N-nitrosophenylhydroxyamine copper salt to 100 parts of the polymerizable component in the water-soluble resin solutions obtained in Synthesis Examples 1 to 3 above.

[0030] Synthetic resin composition 9 was placed in a 100ml glass bottle.
The headspace above the liquid was filled with air and sealed with a plastic tin-lined lid. The bottle was then placed in a hot air dryer maintained at 60°C. The stability of each composition was tested daily by inverting each bottle. When solid resin remained at the bottom of the bottle or when a gel-like substance was found, it was determined that the composition had gelled, and the experiment was stopped, but this synthetic resin composition No gel-like substance was observed. Examples 2 to 4 and Comparative Examples 1 to 4 Using the water-soluble resin solutions A to C obtained in Synthesis Examples 1 to 3, predetermined amounts of salt (B) and polymerization inhibitor shown in Table 1 were added,
A synthetic resin composition was obtained, and the same test as in Example 1 was conducted.

[0031] The symbols a to h in Table 1 are the following salts (B
) and polymerization inhibitor.

[0032]

[Table 1]

[0033]

[Table 2]

From Table 1, it was confirmed that the synthetic resin compositions of Examples 1 to 4 of the present invention had much better storage stability than conventional compositions.

[0035]

Effects of the Invention Since the synthetic resin composition of the present invention uses a salt of N-nitrosohydroxylamine as a polymerization inhibitor, it has better storage stability than a composition containing a conventional polymerization inhibitor. It has a particularly remarkable effect of being superior.

Claims (3)

[Claims] Claim 1: An epoxy vinyl ester resin (A) having an amine salt or ammonium salt of a carboxyl group in the molecule, and a salt of N-nitrosohydroxylamines (
A synthetic resin composition comprising B). 2. The composition according to claim 1, wherein the salt of N-nitrosohydroxylamines (B) is a metal salt of N-nitrosohydroxylamines. 3. The composition according to claim 1, wherein 0.01 to 3.0 parts by weight of the salt of N-nitrosohydroxylamines (B) is used based on 100 parts by weight of the solid content of the epoxy vinyl ester resin (A). .